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Module-1
Corrosion Science and Engineering
Definition

Destruction of metal (or) alloy by the electrochemical reaction when it is exposed to the
external atmosphere. In general, corrosion means formation of oxide layer.

Electrochemical theory of corrosion

According to Electrochemical theory of corrosion, when a metal such as iron exposed to
air, minute galvanic cells are formed. i, e anodes and cathodes are formed.
At Anode: At anodic area, oxidation takes place resulting in corrosion of iron
Fe → Fe2+ + 2e
At cathode: Electrons flow from the above anodic area to cathodic area resulting in reduction
reactions in presence of moisture to OH- and H2 gas.
There are three ways by which reduction takes place depending on the nature of corrosive
environment.
a. If the medium is aerated and neutral
2H2O + O2 + 4e → 4OH−
b. If the medium is deaerated and neutral
2H2O + 2e → H2  + 2OH−
c. If the medium is deaerated and acidic
2H+ + 2e → H2
The following three electrochemical changes occur

a. Formation of large number of minute galvanic cells (anodic and cathodic areas)
b. Corrosion of metal (oxidation) takes place at the anodic area.
c. Reduction of oxygen in presence of water (moisture) to hydroxyl ions and other related
reduction processes at the cathode area.
The metal ions formed at anode (Fe+2) combine with the OH- ions liberated at the cathode
to form the corrosion product and it is accumulated at the junction of anodic and cathodic
areas.
2Fe2+ + 4OH− → 2Fe (OH)2

4Fe(OH) 2 + 2H2O + O2 2[Fe2O3.3H2O]

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Factors that affect the rate of corrosion

1. Anodic and cathodic areas

Small anodic area Small cathodic

area
exposed
Sn plating exposed
Zn plating

Fe(anode)
(large Fe(cathode) (large anodic
cathodic

(a). Rapid corrosion at (b) Slow corrosion at thearea)

small
area)
small anodic area exposed area of Fe

Case i. Larger ratio of cathodic to

anodic area Case ii. Larger ratio of anodic to cathodic
area
The rate of corrosion is highly influenced by the relative area of anode and cathode.

Case i: When tin (Sn) is coated on iron, even if a pinhole is formed, it leads to small anodic area
(Fe) and large cathodic area (Sn). The larger cathodic area demands more electrons for reduction
and this electron has to be supplied by a small anodic area. Hence the rate of corrosion is high.

Case ii: If Zn is coated on iron, Zinc being anodic to iron, even if the coating peels off at certain
places, corrosion would not be intense. Therefore, larger anodic area and small cathodic area
leads to lesser rate of corrosion.

2. Nature of Corrosion product

The corrosion product formed on the surface of metal largely decides the rate of further
corrosion.

Case i: If the oxide layer is porous, conducting, volatile and non-stoichiometric then it acts as
non-protective film. In such case the fresh metal is exposed for further attack. Hence corrosion
takes place continuously. For eg. Iron.
Iron forms iron oxide on its surface which is destructive oxide layer.
Case ii: If the corrosion product formed is insoluble, stable, uniform, non-porous, non-
conducting, and nonvolatile. It acts as a protective film and prevents further corrosion of metal
because it acts as barrier between the fresh metal surface and the corrosive environment. For eg.
Al.
Aluminium forms insoluble oxide layer (Al2O3) on its surface, which is protective film.

3. Nature of medium
1. pH
In general, lower the pH i.e., more acidic the condition, higher is the rate of corrosion.
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For example, in the case of iron,

• If the pH is less than 3, corrosion will be intense.
At this condition, severe corrosion occurs even in the absence of air, due to the
continuous evolution of hydrogen at the cathodic region.
This is because, more H2 evolution, more electron acception at cathode which in
turn more electron release from anode. Hence the rate of corrosion is high.
• If the pH is > 10 i.e., in highly alkaline medium, corrosion practically ceases.
This is because of the formation of protective coating of insoluble layer of
hydrous oxide.
• If the pH is between 3 and 10, corrosion takes place in the presence of oxygen.
If above is the condition, corrosion is negligible in absence of oxygen.
For eg. Ships submerged in deep sea water for hundreds of years remains almost
unaffected.
However, Al and Zn are exceptional cases undergo faster corrosion with high pH.
But in some cases, if pH is in between 3 & 10, corrosion occurs only in presence of O2.

2. Conductivity: Rate of corrosion increases with the increase in conductivity of the medium.
Higher the conductivity of the medium, faster the ions can migrate between the anodic and
cathodic regions. This facilitates higher corrosion rate.

For example, near industrial areas, the atmosphere contains corrosive gases like CO2, H2S, SO2,
HCl and H2SO4 fumes. In presence of these gases, the acidity of the liquid adjacent to the
metal surfaces increases and its conductivity increases. As a result, corrosion increases.
Similarly, in the marine atmosphere, the presence of sodium and other chlorides leads to
increased conductivity of the liquid layer in contact with the metal surface, thereby increases
corrosion.
For another example, the rate of corrosion is
more in the
i) Clayed and mineralized soils than those in
dry sandy soils
ii) Ocean water than the river water.
3. Temperature: Higher the temperature, higher is the rate of corrosion, due to increase in the
ionic conductivity of the corrosive medium and thereby diffusion rate. As temperature increases
passivity decreases which in turn increases the corrosion rate.

Types of corrosion

1. Differential metal corrosion

2. Differential aeration corrosion
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1. Differential metal corrosion

e flow
e flow
O2 from
O2 from
Fe Cu
Fe Ag Atmosphe
Atmosphe re
re O2 in Aerated solution
O2 in solution Aerated solution
solution
of NaCl
OH- of NaCl
-
OH
Corrosion product Corrosion product
Fe2+
Fe2+
-
OH
Case 1 OHCase
- 2
Fig. Differential metal corrosion
This type of corrosion occurs when two different metals are in contact with each other.
Corrosion takes place due to the difference in the potential at the two electrodes. The metal
which is placed higher in the electrochemical series, acts as anode and undergoes corrosion.
Case 1: When Fe coupled with Ag, the rate of corrosion is high due to high potential difference
between the two metals.
Case 2: When Fe coupled with Cu, the rate of corrosion is less due to less potential difference
between the two metals.
The reactions may be :
At anode: M → Mn+ + n e-
At cathode: 2 H2O + O2 + 4 e- → 4 OH-
For illustration, when screws & washers and bolts & nuts are made of different metals,
then the foresaid type of corrosion takes place.

2. Differential aeration corrosion

In this type of corrosion, same metal is exposed to different concentrations of
oxygen.
Half-immersed iron piece Atmospheric

air
Cathodic area O2+2H2O

e + 4e
Corroded part-Anodic area

Aerated solution of NaCl

Fe2+

2+
Fe 4OH -
Fig. Differential aeration corrosion

This type of corrosion occurs when different parts of a metal are exposed to different
concentrations of oxygen. When an iron rod is half immersed in water, the part which is above
the level of water is exposed to atmospheric O2 and hence is more aerated. This part acts as
cathode.
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The part that is immersed in water is exposed to O2 dissolved in water and hence is less
aerated. This part acts as anode and corrosion starts here. Thus corrosion begins at the bottom
portion of the rod. (From B to A)
Other examples are corrosion at barbed wires or corrosion at joints in cross wires.
At anode : Fe → Fe2+ + 2 e-
(oxidation)
At cathode : 1/2 O2 + H2O + 2 e- → 2 OH
-
(Reduction)
Fe2+ + 2 OH- Fe (OH)2 
2Fe (OH)2 + 1/2 O2 + H2O → 2 Fe(OH)3 → Fe2O3+ 3 H2O Fe2O3.xH2O(rust)

a) Water line corrosion

It is a differential aeration corrosion observed in water storage tanks, ships etc.

Oxygen
Water-line Cathodic
areaCorroded
part

(anodic area)

Fig. Waterline corrosion

In steel tanks half filled with water, the portion which is above the level of water is
exposed to atmospheric O2 and hence is more aerated. This part acts as cathode and undergoes
less corrosion.
The bottom portion is exposed to O2 dissolved in water, hence acts as anode and
undergoes more corrosion. Therefore, corrosion begins at this portion and moves slowly upwards
until the entire tank corrodes.

b) Pitting corrosion
Cathodic region Rust
O2 + 2H2O + 4e → 4OH-

Dust

S
Pi t
Anodic region t

Fe→Fe2+ + 2e e
Fig. Pitting Corrosion
e
When dust settles on the surface of a metal, the portion of the metal covered by dust is
l
less aerated and acts as anode, where the rate of corrosion is high. The rest of the metal is
exposed to atmosphere and is more aerated. This portions acts as cathode, where the rate of
corrosion is less.
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This leads to a small anodic area and large cathodic area. The large cathodic area requires
large number of electrons for reduction. This has to be supplied by small anodic area and hence
corrosion takes place fast. This localized corrosion leads to formation of a pit. This type of
corrosion is called pitting corrosion.

Corrosion control

1. Anodizing
This method of corrosion control is adapted for metals which form protective oxide
layer on their surface. Eg.Al.

When Al made as anode in aqueous solution of chromic acid (or sulphuric acid), Al
undergoes oxidation and forms a thin and compact layer of Al2O3. It forms protective layer on
the metal surface. This phenomenon is known as anodizing ( or anodic oxidation).

Anodizing method

In this method,
1.The article (Aluminium) which is to be coated is degreased, polished and connected to the
anode
2. Electrolyte used is 5-10% chromic acid ( Cr2O7 -2+ H2SO4)
3. Temperature: 350C maintained.
4. Potential is applied, gradually increased from 0-40V during first 10 min. Hold the potential
constant at 40V for another 20 min. Then potential is increased to 50V maintain this for next
five minutes.
5. Then the following reaction occurs
At anode: Al Al3+ + 3e x 2
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2 Al3+ + 3H2O Al2O3 + 6H+

At Cathode: 6H+ + 6e 3H2
Net cell reaction: 2Al + 3H2O Al2O3 + 3H2 

6. An opaque oxide layer of 2-8µm thickness is obtained.

7. Applications:
a. Because of its attractive finish and environmentally safe nature, anodized Al is most widely
used in industrial, commercial and domestic material.
b. Anodized articles are used as soap box, window frames, tiffin carriers etc.
c. In household utensils, name plates and decorative objects.

2. Cathodic protection
In this method, corrosion of a metal is controlled by supplying electrons externally so that
the metal acts as cathode.
I. Sacrificial anodic method
Zn strips
Ground

Underground oil pipe

In this method, the base metal is combined with a metal, which is anodic to the base metal.
Zn, Mg, Al, are the common auxiliary anodes used in this method. These metals being more
active act as anode and undergo preferential corrosion, protecting the metal structure. Since
anodic metals are sacrificed to protect the metal structure, this method is known as Sacrificial
anodic method.
For illustration; iron is combined with zinc.
Zinc provides electrons and corrodes; Iron becomes cathode and is protected. However, zinc
has to be replaced from time to time.
For eg., 1. Magnesium block connected to a buried oil storage tank.
2. Zinc bars are fixed to the sides of ocean-going ships to act as sacrificial
anodes.

II. Impressed voltage method

In this method, an impressed current is applied in opposite direction to nullify the corrosion
current and convert the corroding metal to cathode.
In this case, the electrons are supplied from (external source) negative terminal of the
battery. For every small distance, DC source (like battery) is connected. Only negative terminal
is connected to the metal which has to be protected.
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Positive terminal is connected to inert anode like resin bonded graphite rod (or platinized
Ti). For eg. Water tanks and oil pipe lines protected from corrosion by this method.

3. Metal coatings

Galvanizing

Iron sheet Rollers Drier Galvanized iron

Organic dil H2SO4 ZnCl2+NH4Cl Molten Zn (450 0C) Excess Zn

solvent
Coating of iron with zinc (anodic to iron) is called galvanizing.
1. The base metal is first degreased with organic solvents
2. It is treated with dilute sulphuric acid to remove any oxide layer that may be present
on the surface. This is called pickling.
3. The metal is washed with water to remove the acid.
4. The metal is treated with a solution of a zinc chloride and ammonium chloride. This
acts as flux.
5. The metal is finally dipped in molten zinc at 4500C when zinc gets coated on the
metal.
6. It is rolled to remove the excess zinc from the surface.

Note: Galvanization process is used to protect iron from corrosion in the form of roofing
sheets, fencing wires, barbed wires, bolts, nuts, nails, screws, pipes, tubes etc.
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Metal Finishing
Definition

The term metal finishing is referred to processes, which are carried out on surface to
bring about modification of surface by depositing another metal or polymer.
These processes include, electroplating, electroless plating etc.

Technological importance of metal finishing

Metal finishing is carried out to impart one or more of the following properties to the surface
1. To impart better corrosion resistance
2. It is done to get metal ornamental and bright surface
3. To impart required thermal and electrical conductivity
4. To increase hardness of the surface
5. To increase abrasion and impact resistance
6. To increase solderability and chemical resistance
7. To impart abrasion and wear-tear resistance

Electroplating

Factors affecting the nature of electrodeposit

1. Current density
• Current density is defined as the current per unit area expressed in mA cm-2.
• At low current density, electron transfer is slow and hence, the ad-atoms find more
favorable positions i.e. kink sites. This leads to good deposit. ( a bright crystalline
deposit)
• Further at high current densities, mass transfer of ions takes place and a non-adherent
deposit is obtained.
• At very high current densities, hydrogen evolution takes place and the deposit becomes
powdery and contains hydroxides and oxides of the metal.
• An optimum current density is preferred for good deposit. (i.e 10-70mAcm-2)

2. Metal ion concentration

• The plating bath contains salt solution of metal to be plated. To improve the nature of
deposit, other electrolytes, complexing agents and additives are added.
• In order to improve the conductivity, other electrolytes having high conductivity are
added.
• In some cases, complexing agents are added to get complex ions, which gives deposits
with improved qualities.
• Complexing agents are added
2+
o When the metal is known to react with the object for e.g., Cu react with Fe object. i.e
to maintain low metal ion concentration.
o To increase the solubility of sparingly soluble salts,
o To reduce the potential for electrodeposit and
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oTo improve the throwing power of electrolyte.

• Most commonly used complexing agents are cyanides and sulphonates.

3. Organic additives
a. Brighteners:
• When the deposit has a size less than the wavelength of the incident light, the light gets
reflected giving brightness to the surface.
• Brighteners help in producing fine-grained deposit of microscopic size. This imparts
brightness to the deposit.
• Brighteners help deposition parallel to the surface and inhibit deposition perpendicular to
the surface. This gives a bright deposit.
• E.g., thiourea, sulphonates.
b. Levelers:
• These are the substances help in uniform deposition even when the object contains
dislocations(Irregular shapes)
• At these regions of dislocation, the levelers get adsorbed and slow down the depositions.
• Thus, an even deposit is obtained.
• E.g., sulphonates (sodium laurylsulphonate)
c. Structure modifiers or stress relievers:
• These are the substances are added to relieve stress due to lattice defects.
• Due to lattice defects, the objects are under stress. If the stress is high, the electroplated
object will have low impact resistance.
• Therefore, stress relievers are added during electroplating.Thus, electrodeposition is rapid
and uniform.
• These modify structure or surface properties and relieve stress otherwise cracks may
develop.
• E.g., Saccharin.
d. Wetting agents:
• These are added to release the gas bubbles (hydrogen) that may be formed during
electrodeposition.
• Otherwise, the gas bubbles get trapped within the plated metal and get released later on
leading to a brittleness.
• E.g., sodium lauryl sulphate
4. pH:
• At low pH, i.e., acidic conditions, liberation of hydrogen gas takes place which gives
burnt deposit (poor deposit).
• At high pH, i.e., basic conditions, formation of insoluble hydroxide coating takes place.
• Therefore, the optimum pH is maintained between 4 and 8 by adding buffer.
5. Temperature:
• At low temperatures, the rate of diffusion of species is low. Thus it decreases the rate of
electrodeposition (i.e poor deposit). But if the coating is not good, some overgrowths can
be seen on the metal surface, which are called dendrites.
• A good deposit with fast rate takes place slightly at elevated temperatures due to high
diffusion rates of ions.
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• However, at very high temperatures, liberation of hydrogen takes place at cathode, which
leads to poor deposit. Also, corrosion of equipment and decomposition of additives takes
place.
• Therefore, a moderate temperature of 35 to 60oC is maintained during electroplating.

Electroplating of Chromium [Hard and decorative]

Requirements Decorative Hard

Electrolytic bath Chromic acid + H2SO4 in (100:1)

proportion
Anode Pb-Sb or Pb-Sn insoluble anodes
Coated with lead oxide (PbO2)
Cathode Object pretreated
Pretreatment: Degreased with organic solvents pickling polishing mechanical
grinding by using SiC drying and rinsing by using deionized H2O.
Current density (mAcm-2) 145-430 290-580
0
Temperature 45-60 C
Current efficiency (%) 10-15 17-20
Applications provides durable and good Extensively used in
finish on automobiles, industrial and engineering
surgical instruments etc. applications.

Electrolytic reactions
Anodic reaction: 2H2CrO4 H2Cr2O7 + H2O
Hydrogen Hydrogen dichromate
Chromate
H2Cr2O7 2H+ + Cr2O7-2
Dichromate ion
H2 O 2H +1/2O2+2e-
+

Cathodic reaction: Cr2O7 + 14H+ + 6e- 2Cr+3 + 7H2O

Cr+3 + 3e- Cr
Chromium

During electroplating of Chromium, Cr (VI) is reduced to Cr (III) and further to Cr (0), which
gets deposited on the object. For a good deposition, the Cr+3 concentration must be low, as +3
state of Cr gives black deposit.
Here Chromium anodes are not used, as it liberates large excess of Chromium in a +3 state.
Hence inert anodes coated with PbO2 are used. Thus PbO2 oxidizes Cr+3 to Cr+6 which in turn
prevents black deposit.
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Electroless plating of Nickel

The plating on a catalytically active surface by using reducing agents and not by using
electricity is called Electrolessplating.
Requirements
Plating bath: Aqueous NiCl2 (20g/dm3) solution
Object: Stainless steel is given an acid treatment (Cu, Fe, Brass can be directly plated)
Reducing agent: Sodium hypophosphite (20g/dm3)
Complexing agent: Sodium succinate (15g/dm3)
Buffer: Acetate buffer
pH: 4.5
Stabiliser: Thiourea
Temperature: 90-930C

The activated surface is dipped in the bath. The following reaction takes place:

Oxidation: H2PO2- + H20 H2PO3- + 2H++ 2e-

Reduction: Ni+2 + 2e- Ni (s)

Overall reaction: Ni+2 + H2PO2- + H2O Ni + H2PO3- + 2H+

The pH of the solution changes as H+ is liberated in the oxidation process of hypophosphite.

This affects the quality and the rate of plating. Therefore, buffers have to be added to maintain
the pH.
The plating does not start until the temperature is about 700C and reaches a maximum rate at
930C. Further rise in temperature leads to decomposition of components of the bath solution.

Applications

1. It imparts excellent corrosion resistance to metal surface.

2. It imparts excellent wear and abrasion resistance.
3. Because of its hardness and abrasion resistance, it is used in automobiles and other industries
such as pumps, pistons and shafts, pressure vessels.
4. It is employed in electronic and computer components.
5. It is extensively used as decorative finish on plastic items.
6. It gives even and uniform thickness even at recesses and at corners and edges.
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Electrolessplating of Copper on PCB

Requirements
Plating bath: CuSO4 Solution
Object: Pretreated article
Pretreatment and activation involves degreasing and etching in acid. It is activated by
dipping in SnCl2 solution containing HCl at 250C followed by dipping in PdCl2.The
surface is dried to get a layer of Palladium.
Reducing agent: Formaldehyde [Methanol]
Complexing agent and exaltant: EDTA (20g/l)
Buffer: NaOH+Roschelle salt
pH: Almost alkaline (11)
Temperature: Maintained about 250C.
Electrolytic reactions
At Anode: 2HCHO +4-OH 2HCOO- + 2H2O + H2 + 2e-
+2 -
At Cathode: Cu + 2e Cu
Net cell reaction: Cu+2 + 2HCHO + 4-OH Cu + 2HCOO- + 2H2O + H2

An important application of electroless copper plating is on Printed circuit boards (PCB’S). In

double side and multilayered board where plating through holes is required, electroless technique
is the best since the holes cannot be electroplated.

Plating process on PCB

The base object in PCB is a plastic material over which layer of copper is coated. Selected
areas are then protected by a photoresist image and the rest of the copper is etched away to
produce the circuit pattern or the track. PCB is then made by drilling holes, followed by
electroless Cu plating through holes.
The plating is carried out at room temperature by dipping the activated plastic board in the bath
solution. The temperature maintained is 250C. The process is continued till a layer of 5-100
micrometer thickness is obtained.
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Copper foil

Insulting base
Copper foil
Etching of copper to produce
tracking

Drilling of holes

Activation of the surface, through hole

Electroless copper plating

Other applications of electrolessplating

1. For plating on non-conductors.
2. As a base for further electroplating.
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Distinguish between Electroplating and Electrolessplating Processes

Requirements Electroplating Electrolessplating

Driving force Electricity Reducing agent

(Autocatalytic redox reaction)

Anode Separate anode is employed No separate anode

Cathode Object to be coated after removing Object to be coated after

surface impurities making its surface
catalytically active

Throwing power Not satisfactory with irregular Good irrespective of

Shape and inside of tube any shape and size.

Applicability Only to conducting materials Both conductors and

semiconductor eg. Plastics.